Supporting Information. Corporation, 1-1 Kurosakishiroishi, Yahatanishi-ku, Kitakyushu , Japan

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1 Supporting Information Facile Fullerene Modification: FeCl 3 -mediated Quantitative Conversion of C 60 to Polyarylated Fullerenes Containing Pentaaryl(chloro)[60]fullerenes Masahiko Hashiguchi,*,1 Kazuhiro Watanabe, 1 and Yutaka Matsuo*,2 1 Fullerene Development Group, Performance Products Division, Mitsubishi Chemical Corporation, 1-1 Kurosakishiroishi, Yahatanishi-ku, Kitakyushu , Japan 2 Department of Chemistry, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo , Japan @cc.m-kagaku.co.jp matsuo@chem.s.u-tokyo.ac.jp S1

2 1. General methods and materials All reactions were carried out under argon or nitrogen atmosphere. Analytical gradient reversed-phase HPLC was performed on an Agilent 1200 series instrument equipped with an ODS column (YMC-Pack ODS-AM, 5 micron, 4.6 x 150 mm). All runs used linear gradients of methanol (solvent A) and toluene (solvent B). The gradient ran from 25% B up to 55% B over 25 min. Flow rate was 1.0 ml/min and routine UV detection was performed at 290 nm. All 1 H and 13 C NMR spectra were recorded on a JEOL JNM-AL 400 NMR spectrometer system. NMR spectra are reported in part per million from internal tetramethylsilane (δ 0.00 ppm) for 1 H NMR and from CDCl 3 (δ ppm) for 13 C NMR. Mass spectra were measured with Agilent1100LC/MS (APPI, Negative mode) equipped on an ODS column (YMC-Pack ODS-AM). Preparative HPLC was performed on a Buckyprep column (Nacalai Tesque Inc., 20 mm x 250 mm) using toluene/methanol (7/3) as eluent (flow rate: 10 ml/min, detected at 290 nm with an UV spectrometer, Shimadzu SPD-6AV). Unless otherwise noted, materials were purchased from Tokyo Chemical Industry Co., Sigma-Aldrich Co., Wako Pure Chemical Industries, or other commercial suppliers and used after appropriate purification. [60]Fullerene (99.5%) was purchased from Frontier Carbon Corporation. Iron(III)chloride was purchased from Wako Pure Chemical Industries and used as received. S2

3 2. Synthesis of 1 To a mixture of C 60 (501 mg, 0.70 mmol) and iron(iii) chloride (1.13 g, 6.97 mmol) was added chlorobenzene (25 ml) at room temperature. After stirred for 2 hours, the reaction mixture was quenched with water (0.5 ml). The resulting solution was passed through a pad of silica gel (eluent: toluene) and the volatiles were removed with rotary evaporator. The crude product contained the desired penta-adduct 1 mainly, and small amounts of polyarylated products as analyzed by HPLC (YMC-Pack ODS-AM) as shown in Figure S1. Purification with HPLC (Buckyprep column, Nacalai Tesque Inc., 4.6 mm ID x 250 mm, monitored at 308 nm, eluent: toluene/methanol = 7/3) gave the title compound C 60 (C 6 H 4 -Cl-4) 5 Cl as orange powder (228 mg, 25%). 1 H NMR (400 MHz, CDCl 3 ): δ (m, 4H, C 6 H 4 ), 7.23 (d, J = 8.8 Hz, 4H, C 6 H 4 ), 7.30 (d, J = 8.8 Hz, 4H, C 6 H 4 ), (m, 4H, C 6 H 4 ), (m, 4H, C 6 H 4 ); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ): δ (2C, sp 3 -C 60 ), (2C, sp 3 -C 60 ), (1C, sp 3 -C 60 ), 75.85(1C, C(sp 3 -C 60 )-Cl), (1C, C 6 H 4 Cl), (4C, C 6 H 4 Cl), (4C, C 6 H 4 Cl), (4C, C 6 H 4 Cl), (4C, C 6 H 4 Cl), (2C, C 6 H 4 Cl), (2C, C 6 H 4 Cl), (2C, C 6 H 4 Cl), (2C, C 6 H 4 Cl), (2C, C 6 H 4 Cl), (2C, C 6 H 4 Cl), (2C), (2C), (2C), (1C, C 6 H 4 Cl), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C+1C), (2C), (1C), (2C), (2C), (2C), (6C), (2C), (2C), (2C), (2C), (2C); APPI-MS (-): calcd for C 90 H 20 Cl 5 [M-Cl]-), ; found, ; Anal. Calcd for C 90 H 20 Cl 6, C 82.28; H, Found: C 81.90; H, Figure S1. HPLC chart for the synthesis of 1 S3

4 <Alternative Synthetic Method using Solvent> To a mixture of C 60 (500mg, 0.70 mmol) and iron(iii) chloride (1.13 g, 6.97 mmol) was added 1,1,2,2-tetrachloroethane (25 ml) followed by chlorobenzene (470 mg, 4.18 mmol) at room temperature. After stirred for 4 hours, the reaction mixture was quenched with water (0.5 ml). The resulting solution was passed through a pad of silica gel (eluent: toluene) and the volatiles were removed with rotary evaporator. The crude product contained the desired-penta adduct 1 mainly, and small amounts of polyarylated products as well as a trace amount of unreacted C 60 as analyzed by HPLC (YMC-Pack ODS-AM) as shown in Figure S2. Purification with HPLC (Buckyprep column, Nacalai Tesque Inc., 4.6 mm ID x 250 mm, monitored at 308 nm, eluent: toluene/methanol = 7/3) gave compound 1 as orange powder (265 mg, 29%). Figure S2. HPLC chart for the synthesis of 1 in 1,1,2,2-tetrachloroethane 3. Synthesis of 2 To a mixture of C 60 (500mg, 0.70 mmol) and iron(iii) chloride (1.13 g, 6.97 mmol) was added 1,1,2,2-tetrachloroethane (25 ml) followed by bromobenzene (650 mg, 4.14 mmol) at room temperature. After stirred for 6 hours, the reaction mixture was quenched with water (0.5 ml). The resulting solution was passed through a pad of silica gel (eluent: toluene) and the volatiles were removed with rotary evaporator. The crude product contained the desired penta adduct 2 mainly, and small amounts of polyarylated products as well as a trace amount of unreacted C 60 as analyzed by HPLC (YMC-Pack ODS-AM) as shown in Figure S3. Purification with HPLC (Buckyprep column, Nacalai S4

5 Tesque Inc., 4.6 mm ID x 250 mm, monitored at 308 nm, eluent: toluene/methanol = 7/3) gave compound 2 as orange powder (245 mg, 23%). 1 H NMR (400 MHz, CDCl 3 ): δ 6.97 (d, J = 8.8 Hz, 2H, C 6 H 4 ), 7.22 (d, J = 8.8 Hz, 2H, C 6 H 4 ), 7.39 (s, 8H, C 6 H 4 ), 7.44 (d, J = 8.4 Hz, 4H, C 6 H 4 ), 7.70 (d, J = 8.4 Hz, 4H, C 6 H 4 ); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ): δ (2C, sp 3 -C 60 ), (2C, sp 3 -C 60 ), (1C, sp 3 -C 60 ), (1C, C(sp 3 -C 60 )-Cl), (4C, C 6 H 4 Br), (4C, C 6 H 4 Br), (2C, C 6 H 4 Br), (2C, C 6 H 4 Br), (2C, C 6 H 4 Br), (4C, C 6 H 4 Br), (4C, C 6 H 4 Br), (4C, C 6 H 4 Br), (2C, C 6 H 4 Br), (2C, C 6 H 4 Br), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C+1C), (2C), (1C), (2C), (2C), (2C), (6C), (2C), (2C), (2C), (2C), (2C); APPI-MS (-): calcd for C 90 H 20 Br 5 [M-Cl]-), ; found, ; Anal. Calcd for C 90 H 20 Br 5 Cl, C 70.37; H, Found: C 70.36; H, Figure S3. HPLC chart for the synthesis of 2 in 1,1,2,2-tetrachloroethane 4. Synthesis of 3 To a mixture of C 60 (501 mg, 0.70 mmol) and iron(iii) chloride (1.13 g, 6.97 mmol) was added 1,1,2,2-tetrachloroethane (25 ml) followed by iodobenzene (850 mg, 4.17 mmol) at room temperature. After stirred for 4 hours, the reaction mixture was quenched with water (0.5 ml). The resulting solution was passed through a pad of silica gel (eluent: toluene) and the volatiles were removed with rotary evaporator. The crude product contained the desired penta adduct 3 mainly, and small amounts of polyarylated S5

6 products as well as a trace amount of unreacted C 60 as analyzed by HPLC (YMC-Pack ODS-AM) as shown in Figure S4. Purification with HPLC (Buckyprep column, Nacalai Tesque Inc., 4.6 mm ID x 250 mm, monitored at 308 nm, eluent: toluene/methanol = 7/3) gave compound 3 as orange powder (221 mg, 18%). 1 H NMR (400 MHz, CDCl 3 ): δ 6.83 (d, J = 8.8 Hz, 2H, C 6 H 4 ), 7.26 (d, J = 8.8 Hz, 4H, C 6 H 4 ), 7.42 (d, J = 8.8 Hz, 4H, C 6 H 4 ), (m, 8H, C 6 H 4 ), 7.64 (d, J = 8.8 Hz, 4H, C 6 H 4 ); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ): δ (2C, sp 3 -C 60 ), (2C, sp 3 -C 60 ), (1C, sp 3 -C 60 ), 75.67(1C, C(sp 3 -C 60 )-Cl), (4C, C 6 H 4 I), (4C, C 6 H 4 I), (2C, C 6 H 4 I), (2C, C 6 H 4 I), (2C, C 6 H 4 I), (4C, C 6 H 4 I), (4C, C 6 H 4 I), (2C), (2C), (2C), (8C, C 6 H 4 I), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C+1C), (2C), (1C), (2C), (2C), (2C), (6C), (2C), (2C), (2C), (2C), (2C); APPI-MS (-): calcd for C 90 H 20 I 5 [M-Cl]-), ; found, ; Anal. Calcd for C 90 H 20 I 5 Cl, C 61.03; H, Found: C 61.02; H, Figure S4. HPLC chart for the synthesis of 3 in 1,1,2,2-tetrachloroethane 5. Synthesis of 4 To a mixture of C 60 (502 mg, 0.70 mmol) and iron(iii) chloride (1.14 g, 7.03 mmol) was added 1,1,2,2-tetrachloroethane (25 ml) followed by fluorobenzene (402 mg, 4.18 mmol) at room temperature. After stirred for 4 hours, the reaction mixture was quenched with water (0.5 ml). The resulting solution was passed through a pad of silica gel (eluent: toluene) and the volatiles were removed with rotary evaporator. The crude S6

7 product contained the desired penta adduct 4 mainly, and small amounts of polyarylated products as well as a trace amount of unreacted C 60 as analyzed by HPLC (YMC-Pack ODS-AM) as shown in Figure S4. Purification with HPLC (Buckyprep column, Nacalai Tesque Inc., 4.6 mm ID x 250 mm, monitored at 308 nm, eluent: toluene/methanol = 7/3) gave compound 4 as orange powder (103 mg, 12%). 1 H NMR (400 MHz, CDCl 3 ): δ (m, 2H, C 6 H 4 ), (m, 8H, C 6 H 4 ), (m, 2H, C 6 H 4 ), (m, 4H, C 6 H 4 ), (m, 4H, C 6 H 4 ); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ): δ (2C, sp 3 -C 60 ), (2C, sp 3 -C 60 ), (1C, sp 3 -C 60 ), 77.17(1C, C(sp 3 -C 60 )-Cl), (2C, C 6 H 4 F), (4C, C 6 H 4 F), (4C, C 6 H 4 F), (4C, C 6 H 4 F), (4C, C 6 H 4 F), (4C, C 6 H 4 F), (2C, C 6 H 4 F), (2C, C 6 H 4 F), (2C, C 6 H 4 F), (2C, C 6 H 4 F), (4C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C), (2C+1C), (2C), (1C), (2C), (2C), (2C), (6C), (2C), (2C), (2C), (2C), (2C); APPI-MS (-): calcd for C 90 H 20 F 5 [M-Cl]-), ; found, ; Anal. Calcd for C 90 H 20 F 5 Cl, C 87.77; H, Found: C 88.07; H, Figure S5. HPLC chart for the synthesis of 4 in 1,1,2,2-tetrachloroethane S7

8 6. The use of non-halogenated arene (toluene) To a mixture of C 60 (503 mg, 0.70 mmol) and iron(iii) chloride (1.13 g, 6.97 mmol) was added toluene (25 ml) at room temperature. After stirred for 8 hours, the reaction mixture was analyzed by HPLC (YMC-Pack ODS-AM). As shown in Figure S6, a complex mixture containing C60 (ca. 30%) was obtained. 100 intensity (a.u.) Time (min) C 60 Figure S6. HPLC chart for the reaction with toluene S8

9 Table 1. Crystal and refinement data for 1. Empirical formula C 60 (C 6 H 4 Cl) 5 Cl C 7 H 8 Formula weight Temperature 293(2) K Radiation MoKα ( = Å) Crystal system Space group P-1 Unit cell dimensions Triclinic a = (18) Å b = (2) Å c = (18) Å α = (2) β = (2) γ = (2) V (Å 3 ) (7) Z 2 Density ρ calc (g cm -3 ) Absorption coefficient (mm -1 ) F(000) 1424 Crystal dimensions (mm 3 ) range for data collection Index ranges -13 h k l 15 Reflections collected / unique / (R int = ) Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6183 / 0 / 288 Goodness-of-fit on F Final R indices [I>2σ(I)] a), b) R1 = , wr2 = R indices (all data) a), b) R1 = , wr2 = Largest diff. peak and hole (e Å 3 ) / a) Σ( Fo Fc )/Σ Fo b) wr2 = [Σω( Fo 2 Fc 2 ) 2 / Σ(ωFo 4 )] 1/2 S9